Composition containing a pyrimidyl halogeno cyanoalkyl sulphide



Patented Jan. 25, 1944 OFFICE COMPOSITION CONTAINING A PYRIMIDYL HALOGENO CYANOALKYL SULPHIDE vGaetano F. DAlelioand Pittsfield, MaSS.,

J amcs W. Underwood,

assignors to General Electric Company, a corporation or New York No Drawingi. Application May 5, 1942, Serial No. 441,862

' Claims.

This invention relates to the production of new materials and more particularly is concerned with new reaction products of particular utility in the plastics and coating arts and which contains, or are produced from, certain halogen compounds hereafter identified. This application is a continuation-in-part of our copending applications Serial Nos. 395,424 and 395,425, filed May 27, 1941, and assigned to the same assignee as the present invention. Serial No. 395,424 has matured into Patent No. 2,317,736, issued April 27, 1943, and' Serial No. 395,425 into Patent No. 2,295,559, issued September 15, 1942.

The halogen compounds used in carrying the present invention into effect may be represented by the following general'formula:

1 R-c \N' BEN i where n represents an integer and is at least 1 and not more than 2, R represents a member of the class consisting of hydrogen and monovalent hydrocarbon and substituted hydrocarbon radicals, more particularly halo-hydrocarbon rad-, icals, and X represents a halogen atom, more particularly a chlorine, bromine, fluorine or iodine atom.

Illustrative examples of radicals that R in the aboveformula may represent are: aliphatic (e. g., methyl), ethyl, propyl, isopropyl, allyl, methallyl, ethallyl, crotyl, butyl, secondary butyl, isobutyL'amyl, isoamyl, hexyl, etc), in-

cluding cycloaliphatic (e. g., cyclopentyl, cyclohydrogen. However, there also may be used in carrying. the present invention into effect chemical compounds such, for instance, as those represented by the formulas:

and, more particularly,

wheren, R and X have the same meanings as given above with reference to Formula. I.

The halogen compounds used in carrying the present invention into effect may be produced in various ways. 1 One suitable method comprises efiecting reaction, in the presence of a hydrohalide acceptor, between equimolecular proportions of a. monomercapto diamino- [(-NHRM] pyrimidine and a, cyano-alkyl dihalide. The reaction advantageously is carried out in a suitable solvent, for example water or a'mixture of water and alcohol. The hydrohalide acceptor preferably is an alkali-metal hydroxide, e. g., sodium or potassium hydroxide. Thereaction may be'represented by the following equation:

ings as given above In this equation n, R

and K have the same meanwith reference to Formula I,

Diamino pyrimidyl alpha-(alpha-chloro Specific examplesot compounds embraced by Formula I that may be used in carrying the present invention into effect are listed below:

Diamino pyrimidyl chloro cyano-methyl sulphides Dlamino pyrimidyl bromo cyano-methyl sulphides 4-ethylamino B-toluido pyrimidyl-2 beta-[alphabromo alpha-cyclohexyl beta, beta-di'-(hy-' droxyphenyl) cyano-ethyll sulphide Diamino pyrimidyl beta (alpha chlorophenyl Diamino pyrimidyl iodo cyan methyl sulphides Diamino pyrimidyl fluoro cyano-methyl sulphides Diamino pyrimidyl alpha-(beta-chloro cyanoethyl) sulphides Diamino pyrimidyl beta-(alpha-chloro cyanoethyl) sulphides I Diamino pyrimidyl beta-(beta-chloro ethyl) sulphides cyanocyanocyanoalphaalphadfi-diamino S-phenyl pyrimidyl-2 memo cyanomethyl sulphide dfi-diamino 5-cyclohexyl pyrimidyl-2 iodo cyanomethyl sulphide ufi-diamino S-chlorophenyl pyrimidyl-2 chloro cyano-methyl sulphide I 2,6-diamino S-ethyl pyrimidyl-4 chloro I cyano- 7 methyl sulphide d-methylamino G-amino pyrimidyl-2 naphthy chloro cyano-methyl sulphide iiJi-di-(methylamino) pyrimidyl-2 chloro cyanomethyl sulphide I 2,6-di-(ethylamino) s-xenyi pyrimidyl-4 bromo cyano-methyl sulphide 4,6-di-(anilin0) pyrimidyl-2' alpha-(beta-chloro cyano-ethyl) sulphide 4,6-di-(iodoanilino) pyrimidyl-2 beta-(alpha- ;vbromo cyano-ethyl) sulphide *ifi-di-(methylamino) 5-hexyl pyrimidyl-2 beta- (alpha-cyclohexyl beta-phenethyl alpha-chloro -cyano-ethyl) sulphide 4; 6-di-(anilino) S-naphthyl pyrimidyl-2 beta- I (beta-tolyl beta-xylyl alpha-chloro cyanoethyl) sulphide 4,6-di-(fluorotoluido) 5-pentyl pyrimidyl-2 alpha- (beta-chloro cyano-ethyl) sulphide 2,6-diamino 5-methy1pyrimidyl-4 methyl chloro cyano-methyl sulphide 4,6-diaminc fi-cyclohei'zenyl pyrimidyl-2 p, chloro cyano-methyl sulphide 4,-anilino fi-chloroanilino' pyrimidyl-2 alpha- (beta-chloro cyano-ethyl) sulphide 4-inethylamino 6-anilino pyrimidyl-2 pha-benzyl alpha-chloro cyano propyl) sulphide cyanothe pyrimidine nucleus.

alpha-chloro cyano-ethyl) sulphides i-xylidino G-naphthylamino pyrimidyl-2 beta- (alpha-phenyl alpha-lode beta-phenyl betae cyclopentyl cyano-ethyl) sulphide i-cyclohexylamino fi-benzylamino pyrimidyl-2 beta-(alpha bromo alpha-bromomethyl betachloronaphthyl cyano-ethyl) sulphide 4-chlorobenzylamino fi-chloroanilino pyrimidyl-2 alpha-(alpha-methyl beta-phenyl beta-chloro cyano-ethyl) sulphide 4,6-di-(cyclohexenylamiho) pyrimidyl-2 chloro cyano-methyl sulphide 4,6-di-(cyclopentylamino) pyrimidyl-2 bromo cyano-methyl sulphide v z-xylidino 5-cycloliexy1 6-toluido pyrimidyl-4 alpha-(alpha-methyl beta-phenyl beta-chloro cyano ethyl) sulphide 2-ethylamino fi-cyclopentyl fi-toluido pyrimidyl-4 beta-(alpha-bromo alpha-cyclohexyl beta-diphenyl cyano-ethyl) sulphide efi-di-(butylamino) 5-benzyl pyrimidyl-2 beta- (alpha-chloro beta-phenyl cyano-propyl) sulphide 1 It will be understood, of course, by those skilled in the art that, in those compounds listed above that are generically named, the.-NHR groups and the thio group may be attached in any arrangement to the symmetrical carbon atoms of Inother words, the term diamino pyrimidyl" includes within its beta,

meaning both the 4,6-diamino pyrimidyl-2 and the. 2,6-diamino pyrimidyl-4 (2,4-diarnino pyrimidyl-6) compounds. I I

The present invention is based on our discovery that new and valuable materials of particular utility in the plastics and coating arts can be producedby effecting reaction between ingredients comprising essentially an aldehyde, including polymeric aldehydes, hydroxy aldehydes and aldehyde-addition products, and a halogenated compound of the kind embraced by Formula I, numerous examples of which have been given above, These new reaction products are not only valuable in themselves, but find particular utility when incorporated into an acid-curing thermosetting resin, for example acid-curing thermosetting phenoplasts and aminoplasts. For

beta (al-.

instance, we may add a soluble, fusible aldehydereaction product of the halogen compound to an acid-curing thermosetting resin and heat theresulting mixture. The aldehydic reaction product accelerates the conversion of the acid-curing thermosetting resin to an insoluble, inziusible state. Or, we may cause the halogen compound itself to react with the acid-curing thermosetting resin and thus accelerate the curing of the resin. Or, we may form a rapidly curing resin by effecting reaction between ingredients comprising a halogen. compound of the kind embracedby Formula I, an aldehyde, including polymeric aldehydes, hydroxy aldehydes and aldehyde-addition products, and a phenol (including phenol itself, cresols. xylenols, etc.) or an amino or amido compound I (including and imido compounds); for instance 2, 4, 6-trla'mino pyrimidine, 2,4,6-triureido pyrimidine, also aminotriazines, e. g., melamine, ammeline, ammelide, melem, melam, melon, triuieido melamine, etc., aminotriazoles, e. g., guanazole, a urea, e. g., urea itselflthiourea, dicyandiamide, etc.

The resin syrups and molding composition of this invention may be stored for long periods without material alteration. In marked contrast,

the prior acid-curing thermosetting resins, more particularly: those containing direct or active curing catalysts such as mineral acids, e. g., hydrochloric, phosphoric, etc., lackedtime or storage stability. This necessitated early use of the material alter incorporating the catalyst.

Further, the molding compositions of this invention cure rapidly under heat and under heat and pressure and have good plastic flow during molding. Hence molded articles of even the most complicated designs can be made rapidly and economically. The cured compositions have good color, excellent water resistance and surface finish and, in general, meet the strength, hardness and other requirements of the particular service application. V

In practicing the present invention the condensation between the reactants may be carried out under acid, alkaline or neutral conditions and at normal or at elevated temperatures. Any substance or catalyst which has an alkaline or an acid nature may be used to obtain the acid. alkaline or neutral condition, for example ammonia, sodium hydroxide, 1 calcium hydroxide, methyl amine, diethyl amine, tributyl amine, ethanol amines, tri-isopropanol amine, etcJ; mixtures of such alkaline substances; inorganic or organic acids such as hydrochloric, sulfuric, phosphoric, acetic, acrylic, crotonio, malonic, etc.; mixtures of such acids; acid salts such as sodium acid sulphate, monosodium phosphate, monosodium phthalate, etc.; basic salts such as ammonium carbonate, potassium carbonate, sodium acetate,

etc; or mixtures oi such salts.

We may condense the components used in practicing this invention under variou conditions. For example, all the components may be mixed together and the reaction caused to proceed under acid, alkaline or neutral conditions. Or, we may form an acid-curing thermosetting resin (e. g., an acid-curing partial condensation product of ingredients'comprising a phenol and an aldehyde, an acid-curing partial condensation product of ingredients comprising an amidogen compound, e. g., melamine, malonic diamide, maleic diamide, urea, thiourea, etc., and an aldehyde), add the herein-described halogen compound thereto and effect furthercondensation. Or, we may first partially condense the'halogen compound with a molecular excess of an aldehyde under acid, alkaline or neutral conditions and then add thereto at least one other aldehydereactable organic compound, e.'g., a phenol, a urea, aniline, etc., and effect further condensation. Also, we may separately partially condense a halogen compound of the kind embraced by Formula I and a difierent aldehyde-reactable organic compound with an aldehyde and then mix the two products of partial condensation and effect further condensation therebetween.

pressure and temperature conditions. The temperature of reaction may vary from room temperature to the reflux temperature or the reactants at reduced, atmospheric or superatmospheric pressures.

In order that those skilled in the art better may understand how the present invention may be carried into effect, the rollowing ilustrative examples thereof ar given. All parts are by weight.

Example 1 I r Parts Urea -Q 30.0- Aqueous formaldehyde (approx. 37.1%

HCHO) 64.8 Aqueous ammonia (approx. 28% NHz) 3.0

Aqueous solution of sodium hydroxide 4,6-diamino pyrimidyl-2 chloro cyano-ethyl sulphide 0.5

were heated together under reflux at the boiling temperature or the mass for 22 minutes. A molding (moldable) composition was made from the resulting resinous syrup by mixing therewith 33.4 parts alpha cellulose in'flock form and 0.2 part of a mold lubricant, specifically zinc stearate. fI'he wet molding compound was dried at 70 C. until sufllcient moisture had been removed to provide a material that could be molded satisiactorily. A well-cured molded product was ob tained by molding a sample or the dried andground molding compound for C. under apressure of 3,500 pounds per square inch. The molding compound showed good plas- Aqueous solution of sodiumhydroxide 4,6-diamino pyrimidyl-Z chloro cyano-ethyl sulphide All of the above ingredients with the exception of the chloro cyano-ethyl sulphide were heated together under reflux at the boiling temperature of the mass for 18 minutes. Thepyrimidine derivative was now added and refluxing was continued for an additional 7 minutes'to cause it to intercondense with the melamine-formaldehyde ,partial condensation product, The resulting 16 hours.

resinous syrup was mixed with 32.4 parts alpha cellulose and 0.3 part zinc stearate to form a molding compound. The wet molding'composition was dried at room temperature for about A sample of the dried and ground molding compound was mofiied into the form" of The components of each reaction product may invention, as readily will be understood'by those skilled in the art as the description of the invention proceeds. These condensation reactions may be carried out under a wide variety or time,

acteristics by immersion in boiling water for 15'.

minutes, followed by immersion in cold water for 5 minutes. The molding. compound showed good plasticity characteristics during molding as-evidenced by the amount of flash on the molded piece.

5 minutes at Phen l Aqueous formaldehyde resin was clear in its Example 3 Parts 4;6-'diamino pyrimidyl-2 chloro cyano-ethyl sulphide 23 Aqueous formaldehyde 3 (approx. 37.1%

-HCHO) 100 were heated together under reflux at the boiling temperature of the mass for a few minutes, yielding a resinous reaction product that cured to an infusible mass when a sample of it was.

heated on a 150 C. hot plate. A satisfactory molding compound that showed adequate flow characteristics during molding was produced by mixing a portion ofv the resinous syrup with an equal weight of alpha cellulose followed by dry--' ing at a low temperature to remove the excess water. "A well-cured molded piece was obtained Example 4 A phenol-formaldehyde partial condensation product was prepared by heating together the following components, with constant agitation,

for 2 hours at approximately 85-90 C.:

' Parts (approx. 37.1% HCHO) 390.0

Sodium carbonate (anhydrous) eA.

' Due to a slight exothermic reaction the temperature rose for a brief period to 96 C. The resinous syrup produced in this manner is identified in the following formula as syrupyphenolic resin";

Parts Syrupy phenolic resin 30.0 4,6-diamino pyrimidyl-2 chloro cyano-ethyl sulphide Glycerine 2.0

The phenolic resin, which initially was dark red in cplorfbecame lighter in color as the pyrimidine derivative lowered the pH of the solution. The reaction mixture was heated slowly under reduced pressure (55 mm. mercury) until an im aci ic? I ing a resinous syrup that is identified in the following formula as urea-formaldehyde syrup:

Parts Urea-formaldehyde syrup 102.0 Reaction product of Example 3 10.7

'These components were heated together under reflux at the boiling temperature of the mass for 2 minutes. The resulting resinous syrup was 'mixed with 34 parts alpha cellulose and 0.2 part zinc stearate to form a molding composition. The wet molding compound was dried at room temperature until sufllcient moisture had been removed to provide a material that could be molded satisfactorily. A sample of the dried and ground molding compound was molded for 8 minutes at 140 C.' under a pressure of 5,600 pounds per square inch. A well-cured molded piece having a well-knit and homogenous structure was obtained. It had good resistance to water. The plasticity of the molding compound during molding was excellent.

Example 6 Parts Melamine 32.0 Aqueous formaldehyde (approx. 37.1%

ECHO) 61.0 Aqueous ammonia (approx. 28% NH:;) 1.5

Aqueous solution of sodium hydroxide were heated together under refluxat the boiling temperature of the-mass for 15 minutes, yielding a resinous syrup that is identified in the following formula as melamineformaldehyde syru Parts Melamine-formaldehyde syrup 96.0 Reaction product of Example 3 5.3

These components were heated together at the boiling temperature of the mass for 4 minutes. A molding compound was prepared by mixing 32 parts alpha cellulose and 0.2 part zinc stearate with the resulting resinous syrup. This compound was dried and ground as described under Example 5. A sample of the ground compound was molded for 5 minutes at 135 C. under a pressure of 6,750 pounds per square inch. A wellcured molded piece having excellent resistance to water was obtained, as evidenced by the fact that it absorbed only 0.77% by weight of water when tested for its water-resistance characteristics as ternal resin temperature of C. was reached.

.The resulting molasses-like liquid resin was poured into a container and heated therein for 48 hours at C. The resin cured to an insoluble and infusible state.- The solidified resin W815 fairly light in color hard, smooth,-homogeneous, and opaque. This latter characteristic was due mainly to the fact that the liquid casting resin had been ins'umciently dehydrated. The solid upper portion where the water could escape..

Example 5 Parts Urea v 30.0 Aqueous formaldehyde (approx. 37.1%

' HCHO) 67.0 Aqueous ammonia (approx. 28% N113)-.-" 3.5 Aqueous solution of sodium hydroxide were heated together under reflux at the boiling temperature of themass for 20 minutes, yielddescribed under Example 2'. The molded product of this example appeared to be slightly better cured than themolded article of Example 5. However, the plasticity of the molding compound during molding was not quite so good as that'of the molding compound of Example 5.

Example 7 Parts Dimethylol urea (commercial grade containing approx. 11% by weight of water) 60.0

Aqueous ammonia (approx. 28% NHa) 3.5

Aqueous solution of sodium hydroxide Water 42.0

were heated together under reflux the boiling temperature of the mass for 20 minutes, yielding a resinous syrup that is identified in the following formula as dimethylol urea syrup:

Parts Dimethylol urea syrup 107.0 Reaction product of Example 3 10.7

These components were heated together at the It will be understood, of course, by those skilled in the art that the reaction between the composuiting syrup by mixing therewith 36 parts alpha cellulose and 0.2 part zinc stearate. The wet [molding compound was dried and molded as described under Example with the exception that a molding time of 5 minutes and a molding pressure of 9,000 pounds per square inch were employed. A well-molded product which was not so resistant to water as to the molded pieces of Examples 5 and 6 was obtained. The plasticity of the molding compound during molding likewise was not quite so good as that of the molding compounds of Examples 5 and 6.

Example 8 Parts Trimethylol melamine (crystalline) 43.0 Aqueous ammonia (approx. 28% NHa) 1.2

Aqueous solution of sodium hydroxide (0.5 N) 1.0 Water 30.4

were heated together under reflux at the boiling temperature of the mass for 5 minutes, yielding a resinous syrup that is identified inthe following formula as trimethylol melamine syrup":

d I Parts ,Trimethylol melamine syrup 76.0 Reaction product ot'Example 3 5.3

that a moldingtime 01' 3 minutes and a molding pressure of 8,000 pounds per square inch were employed. The molded article was well cured and hadvery good resistance to water, as shown by the fact that it absorbed only 1.63% by weight of water when tested for its water-resistance characteristics as described under Example 2.

The plasticity of the molding compound during molding was very good, being about the same as that or the molding compound of Example 6.-

Example 9 Parts l-phenyl guanazole 35.0 Aqueous fozmaldehyde (approx. 37.1%

HCHO) 32.4

Aqueous solution oi sodium hydroxide (0.5 N) 0.8 Aqueous ammonia (approx. 28% NHa) 1.2 Reaction product of Example 3---, 10.7

were heated together in an open reaction vessel for 3 minutes, at the end of which period oi.'

time separation or a resinous mass took place. The reaction mixture was mixed with 23 parts alpha cellulose and 0.1 part zinc stearate to form a molding compound. The wet molding composition was dried and molded as described under Example 5with the exception that a molding time of 5 minutes was used. The molded article was well cured and absorbed only 0.94% by weight of water when testedfor its water-resists ance characteristics as described under Example 2. The molded piece had a well-knit and homogeneous structure. The plasticity of the moldnents may be effected at temperatures ranging, for example, from room temperature to thefusion or boiling temperature of the mixed, reactants or of solutions of the mixed reactants,

the reaction proceeding more slowly at normal temperatures than at elevated temperatures in accordance with the general law. of chemical reactions. Thus, instead of effecting reaction between the ingredients of the above. examples under reflux at boiling temperature as mentioned in the individual examples, the reaction between the components may be carried -out at temperatures ranging, for example, from room temperature up to the boiling temperature or the mass using substantially long'erreaction periods.

It also will be understood by those skilled inthe art that our invention is not limited to condensation products obtained by reaction of in-- gredients comprising an aldehyde and the spe-' cific halogen compound named in the above illustrated examples. Thus, instead 01' using 4,6- diamino pyrimidyl-'2 chloro cyano-ethyl sulphidewe may use, for example, 2,6-diamino pyrimid-. yl-4 chloro cyanoethyl sulphide, other diamin'o pyrimidyl halogeno cyano-ethyl sulphides (e. g.,-

a. diamino pyrimidyl bromo cyano-ethyl sulphide, a diamino pyrimidyl iodo cy'ano-ethyl sulphide,- a diamlno pyrimidyl fluoro cyano-ethyl sulphide,-. the diamino groups being either in the 4,6 or the 2,6 positions), a diamino pyrimidyl halogeno. cyano-methyl sulphide (e. g., a diamino'pyrimidyl chloro cyano-methyl sulphide, a diamino pyrimidyl bro no cyano-methyl sulphide, etc.) or any other halogencompound (or mixture thereof) embraced by Formula I, numerous specific examples of which have been given hereinbefore. 3

In producing these new condensation products the choice of the aldehyde is dependent largelyupon economic considerations and upon the par-,-

ticular properties desired in the finished prod-- ing compound during molding was excellent, be-

ing about the same as that of the molding c0 m pound of Example 5. a

not. We prefer to use as the aldehydic reactant formaldehyde or compounds engendering formal-. dehyde, e. g., paraformaldehyde, hexamethylene tetramine, etc. Illustrative examples of other aldehydes that may be used areacetaldehyde, propionaldehyde, butyraldehyde, acrolein, methacrolein, crotonaldehyde, heptaldehyde, .octaldehyde, benzaldehyde, iurfural, hydroxy aldehydes (e. g., glycollic aldehyde, glyceraldehyde, etc.)., mixtures thereof, or mixtures of formaldehyde (or 1 compounds engenderlng formaldehyde) with such aldehydes. Illustrative examples of aldehyde-addition products that may be employed instead of the aldehydes themselves are the monoand polymethylol derivatives of urea, 'thiourea, sclenourea and iminourea (numerous examples of which are given in DAlelio copending application Serial No. 377,524, filed February 5, 1941), monoand poly- (N-carbinol) derivatives oi! amidesof poly-carboxylic acids, e. g., maleic, itaconic, fumaric, adipic, malonic, succinic, citric, phthalic, etc., monoand poly-(N-carbinol) derivatives ofthe' aminotriazinesof the aminotriazoles, etc. Particularly goodresults .are obtained with active vmethylene-containing bodies such as a methylol urea, more particularly monoand .di-methylol ureas, and a methylol aminotria'zine, more particularly a methylol melamine, including mono-; methylol melamine and polymethylol melamines (di-, tri-, tetra-, pentaand hexa-methyol melamines). Mixturesoi aldehydes and aldehydeaddition products may be employed, e. g., m'ixtures of formaldehyde and methylol compounds such, for instance, as dimethylol urea, trimethylol melamine, .hexamethylol melamine, etc.

- The ratio of the aldehydic reactant to the halogen compoimd may be varied over a wide range depending, for example, upon the particular properties desired in the final product and the particular halogen compound used as a starting reactant. Thus, we may use, for example, from 0.5 to 8 or 9 Or more mols of an aldehyde for each mol of the halogen compound. When the aldehyde is available for reaction in the form of an alkylol derivative, 'more particularly a methylol derivative such, for instance, as dimeth-- ylol urea, trimethylol melamine, etc., then higher amounts of such aldehyde-addition products ordinarily are used, for example from 1 to or or more mols of such alkylol derivative for each moi of thehalogen compound.

When the halogen compound of the kind embraced by Formula I is used primarily as an intercondensable curing reactant for accelerating the conversion of acid-curing thermosetting resins to an insoluble, infusible state, only a relatively small amoimt of the halogen compound ordinarily is required, for example an amount corresponding to from 0.2 or 0.3% to 5 or 6% by weight ofthe resin to be cured, calculated on the basis of the dry resin. In some cases it may be desirable to use higher amounts, for instance up to 8 or 9 or more parts by weight of the halogen compound per 100 parts (net dry) of the acidcuring thermosetting resin. When the halogen compound of the kind embraced by Formula I is incorporatedinto the acid-curing thermosetting resin in the form of a soluble, fusible aldehyde-reaction" product thereof, then higher amounts of such reaction product ordinarily are ascompared with the amount employed when using the halogen compound itself. The halogen compound or its partial reaction prodnet with anfaldehyde may be: incorporated into .the acid-curing thermosetting resin-either prior to, during or after the formation of the resin or prior to, during or after the formation of a moldin: composition containing the acid-curing thermosetting resin.

Examples of acid-curing thermosetting resins;

the curing of which is accelerated by the halogen compounds herein described or by their soluble, fusible aldehyde reaction products, are the acidcuring phenol aldehyde resins, aminotriazinealdehyde (e. g., melamine-formaldehyde resins), aminotrlazole aldehyde resins, triamino= dissing-aldehyde Y resins, urea-aldehyde I resins, (e. g'., urea-formaldehyde resins), urea-amino= alanine-aldehyde resins .(e. g.. mea -melamine amine, triureido melamine, ammeline, ammelide, melem, melam, melon, triaminopyrimidines, amino triazoles, etc Suitable mixtures of such com-' pounds also may be used. 1

Phenol itself and various substituted phenols, for example the cresols, the xylenols, etc., may be condensed with aldehydes, e. g., formalde- .hyde, furfural, mixtures of formaldehyde and furfural, etc., to form acid-curing thermosetting resins of the phenoplast type, and these thermosetting resins then can be cured to the insoluble and infusible state with the aid of the herein-de scribed halogen compounds or with the soluble, fusible aldehyde-reactioh products thereof.

If desired, the fundamental reaction products of this invention may be modified by introducing other bodies before, ,during or after condensation between the primary components. Numerous examples of modifying agents that may be employed are given, for instance, in D'Alelio and Holmes Patent No. 2,265,688, issued Dec. 9,

1941, page 3, column 2, lines 53-75, page 4, column 1, lines 1-40, which patent is assigned to the same assignee as the present invention.

Thermosetting molding compositions comprising a .filler and an acid-curing thermosetting resin carrying a curing agent comprising a. halogen compound of the kind described herein, or a soluble, fusible aldehyde-reaction product of such a halogen compound, may be molded into a variety of shapes under heat and pressure, more particularly at temperatures of the order of'100" to 200 0., preferably from approximately 120 to 180 C. The molding compositions show good plastic flow during molding since the curing agent not only functions as such butv also gen. erallyserves to impart improved plastic flow to the molding composition. Molded articles of manufacture comprising the molded heat-hardened molding compositions of this invention have a good surface finish, show no evidence of "bleeding of the curing agent, are well cured V throughout, and show no loss in any of their other useful properties due to the presence of the hereindescribed halogen compound or aide-- hyde-reactlon product thereof.

What we claim as new and desire to secure by Letters Patent of the United States is:

,1. A composition comprising an acid-curing, thermosetting resin carrying a curing agent therefor comprising a compound selected from the class. consisting of (1) compounds corresponding to the general formula where n represents an integer and is at least 1 and not more than 2, It represents a member of the class consisting of hydrogen and monovalent hydrocarbon and halo-hydrocarbon radicals, and X represents a halogen atom; and (2) soluble, fusible aldehyde-reaction products of the compounds of (1).

2. A composition comprising an acid-curing, thermosettins, phenol-aldehyde resin having in--. corporated therein a compound corresponding to the general formula A (l; --s-[c..Ri.-1x(cN 1 (anni ti where n represents an integer and is atleast 1 IS" and not more than 2, R. represents a member of the class consisting of hydrogen and monovalent hydrocarbon and halo-hydrocarbon radicals, and X represents a halogen atom.

3. A composition comprising an acid-curing,

thermosetting, amidogen-aldehyde resin having incorporated therein a compound corresponding to the general formula where n represents an integer and is at least- 1 and not more than 2, R represents a member of the class consisting of hydrogen and monovalent hydrocarbon and halo-hydrocarbon radicals, andXrepresentsahalogen atom.

4. A composition comprising the product of reaction of ingredients comprising an aldehyde and a compound corresponding to the general where n represents an integer and isat least 1 and not more than 2, R represents a member of the class consisting of hydrogen and monovalent hydrocarbon and halo-hydrocarbon radicals,

and X represents a halogen atom.

5. A composition as in claim 4 wherein the aldehyde is formaldehyde.

6. A composition comprising the product of reaction of ingredients comprising a phenol, an

aldehyde and a compound corresponding to the general formula 4 where n represents an integer and is at least 1 and not more than 2, R represents a member of the class consisting of hydrogen and monovalent hydrocarbon and halo-hydrocarbon radicals, and X represents a halogen atom.

I. A composition comprising the product of reaction of ingredients comprising a urea, an aldehyde and a compound corresponding to the general formula where n represents an integer and is at least 1 and not more than 2, R represents a member of the class consisting of hydrogen and monovalent hydrocarbon and halo-hydrocarbon radicals, and X represents a halogen atom.

8. A heat-curable resinous condensation prodnot of ingredients comprising urea, formaldehyde and a compound represented by mula 11-0 N m m? the general forwhere n represents an integer and is at least 1 and not more than 2, and X represents a halogen atom.

'9. A product comprising the cured resinous condensation product of claim 8. 10. A condensation product as in wherein X represents a chlorine atom.

11. A condensation product as in wherein X represents a bromine atom. 12. A composition comprising the product of reaction of ingredients comprising melamine, formaldehyde and a compound corresponding to the general formula 'where n represents aninteger and is at least 1 and not more than 2, and X represents a halogen atom.

product of reaction of (1) a partial condensation product of ingredients comprising a phenol and an aldehyde, and (2) a compound corresponding to the general formula where n represents an integer and is at least 1 and not more than 2, and X represents a' halogen atom.

14. A composition comprising the resinous product of reaction of (1) a partial condensation product of ingredients comprising a urea and an aldehyde, and (2) a compound corresponding to the general formula where n represents an integer and is at least 1 and not more than 2, and X represents a halogen atom.

15. A composition comprising the product .of

reaction of ingredients comprising an aldehyde and a diamino pyrlmidyl halogeno cyano-ethyl sulphide.

16. A resinous compositidn comprising the product of reaction of (1) a partial condensa- 19. The method of preparing now condensation I products which comprises efiecting reaction beclaim 8 a claim 8- resinous 13. A composition comprising the resinoustween ingredients comprising an aldehyde and a compound corresponding to the general formula hydrocarbon and halo-hydrocarbon radicals, and

X represents a halogen atom.

20. The method which comprises eflecting partial reaction between ingredients comprising urea and formaldehyde under alkaline conditions, adding to the resulting condensation product a. small amount of a diamino pyrimidyl halogeno cyano ethyl sulphide, and causing the said sulphide to intercondense with the said partial condensation product.

GAETANO F. DALELIO. JAMES W. UNDERWOOD.

CERTIFICATE OF CORRECTION.

January 25, 19th. GAETANO F. DIALELIO, ET AL.

Patent No. 2,5Lo,1o7.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Page 1, first column, line-5 for "contains? read -contain line 511., after "methyl" strike out the closing parenthesis; page 5, first column, line 11, for "and under" read -or under+; page h, second column, line 55, for "melamineformaldehyde"v read .melamineformaldehyde--; line 65, before "0.5 N)" insert an opening parenthesis; page 5, first column, line 10, after "as" strike out "to"; and second column, line. 25, forillustrated" read -il lustrative page 6, first column, line b8, after"'resins strike out the period and insert instead a comma; line 65, and second column, line 1, after "etc"- insert a period; and'that the said Letters Patent'should be read with this correction therein thatthe same may conform to the rec- 0rd of the case in the Patent Office.

Signed and sealed this 9th day of May, A. 1). 191 1;.-

Leslie Frazer (Seal) Acting Commissioner of Patents. 

